Production of color photographic images



Patented Mar. 30, 1954 PRODUCTION OF COLOR PHOTOGRAPHIC IMAGES Jacob Joseph J ennen, Antwerp, Belgium, assignor to Gevaert Photo-Producten N. V., Mortsel, Belgium, a Belgian company No Drawing. Application November 22, 1949, Serial No. 128,913

Claims priority, application Great Britain November 23, 1948 8 Claims. 1

This invention relates to a. process for the production of color photographic images by color development in the presence of a color coupler, to photographic developers, photographic material containing such couplers, and photographic images obtained by such a process.

It is known that a colored image may be formedv by developing a reducible silver salt image in the presence of a compound which during the development couples with the oxidation product of the developing agent and forms a dyestufi which is deposited on the developed silver grains.

To develop magenta dyestuff images, compounds have hitherto been used which contain an active methylene group such as pyrazolones and cyanacetic acid derivatives.

I have now found that a magenta image may also be obtained when a compound is used as a color coupler which does not contain such. an active methylene group.

It is an object of my present invention to provide a new process for the production of color photographic images by color development.

A further object of this invention is to provide new photographic developers containing a color coupler.

Another object of the invention is to provide new photographic material containing a color coupler.

Further objects will appear from the following description.

According to my invention, a reducible silver salt image is developed with a primary aromatic amino developing agent in the presence of a compound corresponding to the following Formula I:

I CC O or to a tautomeric form thereof, corresponding, for instance, to Formula II or III or polycyclic.

aromatic nucleus may be isocyclic, heterocyclic The polycyclic nucleus completed by Z may contain at least one further -NH-NH-CO- group so as to have a double indazolone compound. The compound, as completed by Z, may-- also contain two or more nuclei linked by a chemical bound or by a bior poly-valent atom or group, such as Bearing in mind that the new color coupler may be represented by Formula II, it is believed that coupling with the oxidation products of the developing agent occurs at the N-atom in ortho-- position to the OH group. This assumption is These formulae are analogous to the formula LV of Baker for 2-substituted indazolone (J.

Chem. Soc., London (1945) 267). By this process, dyestufi images may be obtained which have an absorption maximum at about 530-580 m Color couplers according to Formula I may be obtained by causing a molecule of water to split off from aromatic, dihydro-aromatic or heterocyclic monoor poly-(orthohydrazino carboxylic acids) according to the method described by I K. Pfannsteil and J. Janecke in Berichte 751 Sometimes, the preparation of one of said hydrazino acids yields directly the corresponding indazolone because the hydrazino acid although occurring at an intermediate stage cannot be isolated.

The color coupler according. to my present invention may also be obtained in a manner anal be written in many tautomeric forms, one of which is represented by the following Formula Most of these color coupler are converted into a yellow product when in an oxidizing medium such as a bath for removal of the silver so that a yellow reversal image, which results from the oxidation of th residual color coupler in the bath for removing the silver, is added to the dyestuff image formed on color development. If this is undesirable, the formation of the yellow product may be avoided by treating the color developed emulsion layer, before removing the silver, with a bath containing formaldehyde, a formaldehyde-yielding compound, or another aldehyde. Such an aldehyde is supposed to react with the --NHNHCO group of the coupler, avoiding in this way any subsequent coupling or formation of yellow oxidation products.

The dyestufis obtained on color development with the color couplers according to the present invention are more stable to acid than those obtained with the known pyrazolones, and those which contain a substituent rendering them fast to diffusion are not removable from the emulsion layer by washing.

The said new color couplers may further .be

used in the developing solution or in a colloid layer, in the latter case either in a lightg-sensitive layer or in a non-light-sensitive layer adjacent to a sensitive layer or separated therefrom by a water-permeable colloid layer.

The aromatic amino compounds which may be used as developing agent in. accordance with the present invention include the mono-, diand tri-amino aryl compounds. Among the monoamino developing agents .may be .mentioned scope thereof.

Example 1 1.1 g. indazolone according to Formula IV:

4 and prepared, for instance, according to K. Pfannstiel and J. Janecke, Berichte '75 (1942) 1104, are dissolved in 20 cc. of an aqueous solution of sodium carbonate 10% and added to cc. of aphotographic silver halide emulsion prepared from 2.75 g.' AgNOs. This emulsion is coated onto a support, exposed and developed in a solution obtained b mixing equal parts of the following solutions:

(A) N,N-diethyl-p-phenylene diamine hydrochloride g 6 Water to cc 500 (B) Potassium carbonate g 75 Potassium bromide g 2.5 Water to cc 500 A magenta dyestuff image with an absorption maximum at 550 nm is formed.

Example 2 1 g. 4-chloro-indazolone according to Formula V:

which has been prepared according to Berichte 75 (1942) 1106 is dissolved in 22 cc. of an aqueous solution of sodium carbonate 5% and added to 100 cc. of a positive photographic silver halide emulsion. This emulsion is coated onto a support, exposed and developed in a solution obtained by mixing equal parts of the following solutions:

(A) N,N-diethyl-pphenylene diamine sulphate g 3.2 Water to cc 500 (B) Potassium carbonate g '75 Potassium bromide g 2.5 Water to cc 500 Amagenta dyestuff image is formed.

Example 3 11 g. 3.5dichloro-2-amino benzoic acid are dissolved in 50 cc. of a concentrated aqueous so- .lution of hydrochloric acid and 350 cc. water.

To this solution are added 100 cc. of an aqueous solution of sodium nitrite 5%. Next, the mixture is added during 10 minutes to 750 cc. of an aque- 1 ous saturated solution of S02 while S02 gas is continuously conducted into said solution. After complete addition, S02; iscQntinued to be introduced for another 30-minutes, whereupon the mixture is boiled during 30 minutes, cooled and filtered with suction. The product obtained is recrystallized With ethanol.

2 g. ofthe indazolone derivative prepared as;

indicated above are dissolvedin 50 cowater and 10 c ran, aqueous solution of sodium hydroxide Melting point 227-,. 228 C. N content calculated 13.79, found 13.50.

2 N and added to 1 litre of a mixture of equal parts of the following solutions:

(A) N,N-diethyl-p-phenylene diamine sulphate g 3.2 Sodium sulfite g 5 Water to cc 500 (B) Potassium carbonate g 75 Potassium bromide g 2.5 Water to cc 500 An exposed positive motion picture film is developed in the developer thus prepared and a magenta. image with absorption maxima at 542 and 581 me is formed.

" Example 4 6 g. 4-nitro-indazolone according to Formula VII:

VII

prepared according to "Berichte 75 (1942) 1105 are dissolved in 100 cc. acetone and 20 cc. of an aqueous solution of sodium hydroxide 2 N and added to 1 litre of a mixture of equal parts of the following solutions:

In the developing solution thus prepared, an exposed positive motion picture fihn is developed and a magenta image with an absorption maximum of 575 m is obtained.

Example 5 8.5 g. 4-sulfo-1-amino benzol-2-carboxylic acid are dispersed in 32 cc. of a concentrated aqueous solution of hydrochloric acid. successively, 64 cc. of an aqueous solution of sodium nitrite 5% are added to the suspension, and then 225 cc. water. The whole is brought slowly into 480 cc. of a solution of S02 while S02 gas is continuously conducted into that solution. After complete addition, S02 is introduced for yet half an hour. Next, the volume of the mixture is reduced to about 150 cc. by evaporation. The mixture is cooled and filtered with suction. The product separated is'recrystallized in a little amount of water. It melts above 300 C. and is believed to be indazolone-5-sulfonic acid corresponding to Formula VIII:

VIII

N content calculated 13.08, found 13.51. S content calculated 14.95, found 15.03.

' 2 g. of this indazolone-S-sulfonic acid are added to a mixture of equal parts of the following solution:'

An exposedpositive motion picture film is developed in the color developer thus prepared and a bluish magenta image is formed.

Example 6 6.6 g. B-amino-indazolone-hydrochloride, prepared according to Berichte (1912) 1107, and 5.1 g. 2-chlorobenzothiazole are dissolved in cc. absolute ethanol. The solution is evaporated on the water bath. The residue is washed by boiling with ether and then with water. The washed residue is dissolved in 200 cc. ethanol. The volume of the solution is reduced to 20 cc. The product which precipitates after cooling is filtered with suction. It melts at 252255 C. After washing by boiling with water and then with acetone, the melting point may be raised to 270-272 C.

S content calculated 11.34, found 12.73.

The product is believed to be 6(2'-benzothiazolyl amino)indazolone according to Formula 2 g. of this indazolone derivative are dissolved in 20 cc. of a methanolic solution of potassium hydroxide N and added to 1 litre of a mixture of equal parts of the following solutions:

(A) N,N-diethy1-p-phenylene diamine sulphate g 3.2 Sodiumsulfite g 5 Water to cc 500 (B) Potassium carbonate g 75 Potassium bromide g 2.5 Water to cc 500 An exposed positive motion picture film is developed in the developer thus prepared and a bluish magenta image is formed. Absorption maximum 576 m Example 7 A solution of 2.2 g. G-amino-indazolone hydrochloride and 3 g. 2-methyl-mercapto benzothiazole dimethylsulphate in 20 cc. pyridine is reiiuxed for 30 minutes and then poured into water. The precipitate is filtered with suction and recrystallized from ethanol. Melting point is 262- a 264 C. The product is believed to be 6(1'- methyl benzothiazolylidene-2') aminoindazolone according to Formula X:

N content calculated 18.85, found 18.16. content calculated 10.77, found 11.26.

0.2 g. of this indazolone derivative is dissolved in 50 cc. alcoholic solution of potassium hydroxide Nand added to 100 cc. of a mixture of equal parts of the following solutions:

(A) N,N-diethyl-p-phenylene diamine sul- By developing an exposed positive motion picture film in the developer thus prepared, a magenta image with an absorption maximum at 567 m is formed.

Example 8 A mixture of 5.5 g. G-aminoindazolone-hydrochloride, 3.7 g. phthalic acid anhydride and 5 cc. pyridine is heated for 30 minutes at 180 C. on an oil bath. The mixture is cooled and the solid mass obtained is washed by boiling with water and next with acetone. Melting point is 304-305 C. N content calculated 15.05, found 14.79. The product is believed to be fi-phthal-imido indazolone corresponding to Formula X1:

0 o o NH \IH l 0.2 g. of this indazolone derivative is dissolved in 50 cc. alcoholic solution of potassium hydroxide N and added to 100 cc. of a mixture of equal parts of the following solutions:

(A) N,N-diethyl-p-phenylene diamine sulfate g 3.2 Sodium sulfit g 5 Water to cc 500 (B) Potassium carbonate g 75 Potassium bromide g 2.5 Water to cc 500 By developing an exposed positive motion picture film in the developer thus prepared, a magenta image is formed.

Example 9 N content calculated 8.41, found 8.32 and 8.40.

l g. of this 7-octadecenyl succinyl aminoindazolone dissolved in 2.5 cc. ethanol and 2.5 cc. of'an aqueous solution of sodium hydroxide 2 N is added to 100 cc. of an emulsion for positive motion picture film. This emulsion i coated on a support, exposed and developed in a solution obtained by mixing equal parts of the following solutions:

(A) N,N-diethyl-p-phenylene diamine sulfate g 3.2 Sodium sulfite g 5 Water to cc 500 (B) Potassium carbonate 2. g 75 Potassium bromide r "g- 2.5 Water to cc.- 500 A magenta image with an absorption maximum at 568 m, is obtained. This coupler does not diffuse. The 4, 5 and 6 octadecenyl succinylamino-indazolones may be prepared and used in the same Way.

Example 10 A solution of 1.1 g. 6-amino-indazolone-hydrochloride and 1.1 g. of the copolymer of styrene and maleic acid anhydride in 5.5 cc. pyridine is boiled for 5 hours. The reaction mixture is washed with boiling water, and then with boiling methanol. A product melting above 300 C. and corresponding to Formula XIII:

XIII

(:IH: CQ\ @r NH (IJHCONH- 4 CHCOOH N wherein x is a positive integer, is obtained.

N content calculated 11.96, found 11.03%.

1 g. of this product is dissolved in 30 cc. of a concentrated aqueous solution of NH3 by heating F on the water bath and added to cc. of an emulsion fOr a positive motion picture film. This emulsion is coated onto a support, exposed and developed in a solution obtained by mixing equal parts of the following solutions:

(A) N,N-diethyl-p-phenylene-diamine sulfate g 3.2 Sodium sulfit g 5 Water to cc 500 (B) Potassium carbonate g 75 Potassium bromide g 2.5 Water to cc 500 A magenta image is obtained. This coupler does not diffuse.

Example 11 3.2 g. S-amino-indazolone hydrochloride prepared according to Berichte 75 (1942) 1107, 6 g. stearic acid chloride and 45 cc. pyridine are refluxed for 5 hours. The residue is washed by boiling first with water, then with acetone and finally with methanol. 5 stearoyl-amino indazolone melting at 218-220 C. and corresponding to- Formula XIV:

XIV

CHa(CH2)mCONH is obtained.

N content calculated 10.12, found 10.03 and 10.20.

1 g. of this product is dissolved in 3 cc. of an ethanolic solution of potassium hydroxide N and 7 cc. methanol and added to 100 cc. of an emulsion for positive motion picture film. This emulsion is coated onto a support, exposed and developed in a solution obtained by mixing equal parts of the following solutions:

(A) N,N-diethyl-p-phenylene diamine sulfate g 3.2 Sodium sulfite g 5 Water to cc 500 (B) Potassium carbonate g 75 Potassium bromide g 2.5 Water to -cc 500 A magenta image with an absorption maximum at 530 m is obtained. This coupler does not diffuse.

Example 12 0.2 g. of the bis-indazolone derivative called hereinafter 5-(indazolonyl-5') -indazolone, corresponding to Formula XV:

c (I) 0 mlr NH \d and prepared according to Gazz. Chim. Ital. 66 (1936) 17, are dissolved in cc. ethanolic solution of potassium hydroxide N and added to a solution obtained by mixing 50 cc. of each of the following solutions:

(A) N,N diethyl p phenylene diamine By developing an exposed positive motion picture film in the developer thus prepared, a bluish magenta image with an absorption maximum at 580 me is obtained.

Example 13 0.2 g. 2-6-dimethyl-4-hydrazino nicotinic anhydride corresponding to Formula XVI:

XVI CH:

. N (I; 0 OH! /NH and prepared according to Berichte 36 (1903) 519 are dissolved in 5 cc. of an aqueous solution of potassium hydroxide N/ and added to a solution obtained by mixing 50 cc. of each of the following solutions:

(A) N,N diethyl p phenylene diamine sulphate g 3.2 Water to cc 500 (B) Potassium carbonate g '75 Potassium bromide g 2.5 Water to cc 500 By/developing an exposed positive motion picture film in the developer thus prepared, a bluish magenta image with an absorption maximum at 579 m is obtained.

Example 14 XVII OH-NH 1 g. of this product is dissolved in cc. of an aqueous solution of potassium hydroxide N/2 and added to 100 cc. of an emulsion for positive motion picture film. This emulsion is coated onto a 10 tained by mixing equal parts of the following solutions:

(A) N,N diethyl p phenylene diamine sulphate g 3.2 Water to cc 500 (B) Potassium carbonate g Potassium bromide g 2.5 Water to cc 500 A violet image is obtained.

Example 15 l g. of the bis-indazolone described as hexahydrobenzodipyrazolone corresponding to Formula XVIII:

XVIII NH CH2 and prepared according to J1. fiir pr. Chemie, [2] 51 (1895) 66, are dissolved in 22 cc. of an aqueous solution of NaOH 2 N and 5 cc. ethyl alcohol by heating and added to cc. of an emulsion for positive motion picture film. This emulsion is coated onto a support, exposed and developed in a solution obtained by mixing equal parts of the following solutions:

(A) N,N diethyl p phenylene diamine sulphate g 3.2 Water to cc 500 (B) Potassium carbonate g 75 Potassium bromide g 2.5 Water to cc 500 A bluish image is formed.

Example 16' To 14 g. diamino diphenyl methane dicarboxylic acid and 40 cc. concentrated aqueous solution of hydrochloric acid, 35 cc. of an aqueous solution of sodium nitrite 10% are added while cooling with ice. The reaction mixture is filtered. The filtrate is added in 30 minutes drop by drop to 400 cc. of a saturated aqueous solution of sulphurous anhydride while cooling with icewater and conducting S02 into the reaction mixture. After complete addition, introduction of S02 is continued for another 30 minutes. 400 cc. water are then added and the whole is boiled for one hour, whereupon the mixture is filtered and the filtrate cooled. The precipitate is recrystallized from ethyl alcohol. The S-methylene-bis- (indazolone) obtained corresponds to Formula XIX:

XIX

(A) N,N diethyl p phenylene diamine hydrochloride g 6 Sodium sulfite g 5 Water to M 500 (B) Potassium carbonate -..g 75 Potassium bromide g 2.5 Water to cc 500 A magenta dyestuff image with an absorption CH C O support, exposed and developed in a solution ob- 5 maximum at 530 me is formed.

1. Process for the production of a colored photographic image, which comprises developing areducible silver salt image a photographic element by means of aprimary aromatic amino developing agent in thepresence Iclaim:

"of a color coupler having a formula selected from the group'consisting of Formula I:

' ,c'oo

and tautomeric forms of Formula I, wherein Z represents the non-metallic atoms required for completing an aromatic nucleus.

2. Photographic developer containing a primary aromatic amino developing agent and a color coupler having a formula selected from the group consisting of For'mulaI:

and tautomeric forms of Formula I, wherein Z represents the non-metallic atoms required for completing an aromatic nucleus.

3. A'photographicdeveloper containing a primary aromatic amino developing agent and 5- (indazolonyl-B') -indazolone.

4. A photographic developer containing a primary aromatic amino developing" agent and 5-methylene-bis-indazolone.

5. A photographic material comprising a silver halide emulsion layer and a colloid layer, containing an octadecenyl-succinyl-amino-indazolone.

6. A photographic material comprising a silver an teutom r c. fo m of o m la I.v wh Z re ent he n n-m atom r ui for co et n an erqm c ucleus,-

JACOB, JOSEPH JENNEN.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 742,405 Eichengrun Oct. 27, 1903 2,200,306 Schneider May 14, 1940 2,213,986 Kendall Sept. 10, 1940 2,353,754 Peterson July 18, 1944 FOREIGN PATENTS Number Country Date 524,557 Great Britain Aug. 8, 1940 577,804 Great Britain May 31, 1946 OTHER REFERENCES Journal of the Chemical Society, vol. 112, I, pages 219-220.

Beilstein, vol. 24, pages 111 and 112 (1936).

Berichte, vol. 13, pages 681 and 682 (1880). 

8. A PHOTOGRAPHIC MATERIAL COMPRISING A SILVER HALIDE EMULSION LAYER AND A COLLOID LAYER, CONTAINING A COLOR COUPLER HAVING A FORMULA SELECTED FROM THE GROUP CONSISTING OF FORMULA I: 